FI90784C - A process for preparing a high molecular weight poly (arylene sulfide ketone) - Google Patents

Abstract

A process, and product produced therefrom, for preparing a high molecular weight (poly(arylene sulfide ketone) from the reaction product of an alkali metal bisulfide with an alkali metal hydroxide, employing molar excess of alkali metal bisulfide with respect to the alkali metal hydroxide. A process, and product produced therefrom, for preparing a high molecular weight poly(arylene sulfide ketone) employing an alkali metal sulfide and an alkali metal hydrosulfide, wherein the alkali metal sulfide is added in a molar excess with respect to the alkali metal hydrosulfide.

Description

i 90784

The invention relates to a process for the preparation of poly (arylene sulphide ketones). In addition, the process relates to poly (arylene sulfide ketones) prepared from the reaction product of an alkali metal hydrogen sulfide and an alkali metal hydroxide. The invention further relates to poly (arylene sulfide ketones) prepared using alkali metal sulfide and alkali metal hydrogen sulfide. The invention also relates to fibers and other products made from these poly (arylene sulfide ketones).

15 Poly (arylene sulfide ketones), PASK, are an important class of technical thermoplastics. Poly (arylene sulfide ketones) are of commercial interest for use in films, fibers, extrudates and composites due to their high melting points. One method of producing poly (arylene sulfide ketones) involves the reaction of a dihalobenzophenone, such as dichlorobenzophenone, with an alkali metal sulfide. The alkali metal sulfide is obtained as a result of the reaction of an alkali metal hydrogen sulfide and an alkali metal hydroxide using practically exact equimolar amounts (stoichiometric 25 amounts) of alkali metal hydrogen sulfide relative to the alkali metal hydroxide, since both components are in excess.

However, the major drawback of poly (arylene sulfide ketones) has been its relatively low molecular weight. It would be preferable to be able to produce poly (arylene sulfide ketones) with a relatively high molecular weight. High molecular weight poly (arylene sulfide ketones) generally have better impact resistance and stiffness compared to low molecular weight poly (arylene sulfide ketones).

It is an object of the present invention to provide a process for the preparation of high molecular weight poly (arylene sulfide ketones). Another object of the invention is to prepare high molecular weight poly (arylene sulfide ketones).

It has now been found that high molecular weight poly-5 (arylene sulphide ketones) are prepared by contacting a polyhalobenzophenone and an alkali metal hydrogen sulphide in the reaction mixture, preferably in a polar solvent, with a small but important alkali metal. måå-10 råån required for condensation polymerization.

The invention thus relates to a process for the preparation of a high molecular weight poly (arylene sulphide ketone) by polymerizing equimolar amounts of polyhalogen-nibenzophenone and an alkali metal sulphide in a reaction mixture, the process being characterized by the fact that the polymerization is carried out when the polymerization is carried out the molar ratio of alkali metal hydrogen sulfide to alkali metal sulfide is 0.004: 1 to 0.038: 1.

20

In the first embodiment, which is presently preferred, the alkali metal sulfide is prepared by contacting the alkali metal hydrogen sulfide with an alkali metal hydroxide in a molar ratio of about 1.004: 1 to 1.038: 1 to give a small excess of alkali metal hydrogen sulfide.

In another embodiment, high molecular weight poly (arylene sulfide ketones) are prepared by contacting polyhalobenzo-phenone, alkali metal sulfide, and alkali metal hydrogen sulfide in a reaction mixture, preferably in a polar solvent, to which is added a solution of: under thiol conditions effective to produce poly (arylene sulfide k-35 ton) again with a certain small excess of alkali metal hydrogen sulfide.

90784 3

In either embodiment or combination thereof, the molar excess of alkali metal hydrogen sulfide is about 0.004 to 0.038, relative to the polyhalobenzophenone, i. in addition to alkali metal sulphide added or formed in situ.

5

The process of the invention provides poly (arylene sulfide ketones) having an intrinsic viscosity of at least about 0.48. This is not to be expected given the importance of stoichiometry in condensation polymerizations.

10

Figure 1 is a graphical representation of the intrinsic viscosity of poly (phenylene sulfide ketones) when poly (phenylene sulfide ketones) is prepared by a condensation polymerization reaction using a small amount of sodium bisulfide (sodium hydrogen-15-diisibide) in (NASH) diis , sodium sulfide (Na 2 S) and N-methyl-2-pyrrolidone (NMP). The area between the longer dashed lines in the figure indicates that poly (phenylene sulfide ketones) with an intrinsic viscosity of at least about 0.55 are obtained when a small molar excess of NaSH in an amount greater than about 1-3.5 mole percent is used in the reaction mixture. , To form Na2S. The range between the shorter dashed lines in the figure indicates that poly (phenylene sulfide diketones) having an intrinsic viscosity of at least about 0.65 are obtained when an excess of about 1.5-3.3 mole percent of NaSH is used in the reaction mixture.

These results are in stark contrast to poly (phenylene sulfide ketones) having an intrinsic viscosity of less than about 0.45 and prepared using alkali metal hydrogen sulfide with alkali metal hydroxide in a stoichiometric molar ratio of about 1: 1 without NaR. , which is about 1.05: 1. Only a small relationship was effective.

3 3

According to the invention, poly (arylene sulfide ketones) are prepared by contacting in the reaction mixture (a) at least one polyhalobenzophenone, (b) at least 4 one alkali metal sulfide, either added thereto or equivalent to a polar alkali metal sulfide or alkali metal hydride solvent.

5

In one embodiment, the alkali metal sulfide used in the process of the invention can be prepared from an alkali metal hydrogen sulfide and an alkali metal hydroxide in aqueous solution using the specified ratios. In another embodiment, the alkali metal sulfide can be used with the alkali metal hydrogen sulfide in aqueous solution. In both embodiments, the amount of hydrogen sulfide is critical to produce high intrinsic viscosity poly (arylene sulfide ketones).

15

In a first embodiment, the reaction of a dihalobenzophenone such as 4,4'-dichlorobenzophenone with an alkali metal sulfide prepared from an alkali metal hydrogen sulfide and an alkali metal hydroxide such as sodium hydrogen sulfide and sodium hydroxide in a polar solvent such as N-methyl-2-pyrr phenylene sulphide ketone) in which the poly (phenylene sulphide ketone) units are repeated may be represented as follows: 25 0 0

NaSH || || 3 0 Cl ^ Cl S -

NaOH L

In another embodiment, a polymerization using di-35 halobenzophenone, such as 4,4'-dichlorobenzophenone, with an alkali metal sulfide, such as sodium hydrogen sulfide, and an alkali metal hydrogen sulfide, such as sodium hydrogen sulfide, in a polar solvent, such as NMP, is repeated to form poly (phenylene sulfide kike-40 ton) can be represented as follows: li 90784 5

O O

NaSH || || 5 + ^ C \ NMP v _ C ^ ^ -.s j§f jof ^

Cl Cl s - io * -

The invention uses a small but substantial molar excess of alkali metal hydrogen sulfide relative to dihalobenzophenone or alkali metal sulfide.

Although the molar excess of alkali metal hydrogen sulfide relative to the alkali metal hydroxide may vary to some extent, generally when alkali metal hydrogen sulfide is used with alkali metal hydroxide to about 20 to about 3 mole percent, its range is from about 0.5 to about 3.8 mole percent. calculated to form alkali metal sulfide. The range of corresponding molar ratios of alkali metal hydrogen sulfide to alkali metal hydroxide is from about 1.004: 1 to 1.038: 1, preferably from about 1.01: 1 to 1.035: 1.

25

In another embodiment of the invention, the alkali metal hydrogen sulfide is used in a range of about 0.4 to 3.8 mole percent, preferably about 1 to 3.5 mole percent, with respect to an amount of alkali metal sulfide of 100 to ensure a small but substantial excess of alkali metal hydrogen sulfide. . The corresponding molar ratio of alkali metal hydrogen sulfide to alkali metal sulfide ranges from about 0.004: 1 to 0.038: 1, preferably from about 0.01: 1 to 0.035: 1.

The intrinsic viscosity of the poly (arylene sulfide ketones) prepared by the methods is at least about 0.48, preferably about 0.55-0.77. Polymers can be widely used in films, fibers, extrudates and composites due to their high melting point and high molecular weight.

40 6

Figure 1 is a graphical representation of the intrinsic viscosity of poly (phenylene sulfide ketones) represented by poly (arylene sulfide ketones) prepared by a condensate reaction in which the molar excess of NaSH to NaOH is about 0-5% in each mole blend of the polymerization. , 4'-dichlorobenzophenone and NMP. The area between the longer dashed lines in the drawing indicates that poly (phenylene sulfide ketones) having an intrinsic viscosity of at least about 0.55 are obtained when a molar excess of NaSH of about 1-3.5 mole percent is used. The shorter dashed lines indicate that poly (phenylene sulfide ketones) having an intrinsic viscosity of at least about 0.65 are obtained using a molar excess of NaSH of about 1.1-3.3 mole percent relative to NaOH. This is in stark contrast to po-15 ly (for arylene sulfide ketones) having an intrinsic viscosity of less than about 0.45 and obtained by combining dihalobenzophenone, alkali metal hydrogen sulfide and alkali metal hydroxide in a stoichiometric ratio of about 1: 1: 1 and greater. which is about 1: 1.05: 1.

20

Polyhalobenzophenone, preferably dihalobenzophenone, is used in the process. Dihalobenzophenones can be represented by the formula:

O

25 11 A- \ x —ø— c - (° y ~ x wherein each X is selected from the group consisting of chlorine, bromine, fluorine and iodine. The polyhalobenzophenones which may be used are 4,4'-dichlorobenzophenone, 4.4 '-di-fluorobenzophenone, 4,4'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,4'-dichlorobenzophenone, 2,4,4'-trichlorobenzophenone, 2,4,4'-triiodobenzophenone, 2 , 4,4'-trifluorobenzophenone, 2,4,4'-tribromobenzophenone and the like and mixtures thereof 35. The presently preferred dihalobenzophenone is 4,4'-dichlorobenzophenone due to its efficacy and commercial availability.

90784 7

Alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. Alkali metal hydrogen sulfides (sometimes referred to as bisulfides) include lithium hydrogen sulfide, sodium hydrogen sulfide, potassium hydrogen sulfide, rubidium hydrogen sulfide, cesium hydrogen sulfide, and mixtures thereof. Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures thereof.

10

The preferred alkali metal sulfide is sodium sulfide (Na; S) due to its effectiveness. The preferred alkali metal hydrogen sulfide is sodium hydrogen sulfide (NaSH) due to its effectiveness.

The preferred alkali metal hydroxide is sodium hydroxide (NaOH) due to its effectiveness.

The molar ratio of dihalobenzophenone to alkali metal sulfide should keep the stoichiometric ratio 1: 1 as close as possible in the condensation polymerization.

20

Suitable solvents for use in the process of the invention include polar organic solvents that can be used with dihalobenzophenone and alkali metal sulfide to produce poly (arylene sulfide ketones). These polar organic solvents include, for example, amides and sulfones. Specific examples of such polar organic solvents include hexamethylphosphoramide, tetramethylurea, N, N'-ethylenedipyrrolidone, N-methyl-2-pyrrolidone (NMP), pyrrolidone, caprolactam, N-ethylcaprolact, N-ethylcaprolactol , diphenylsulfone and the like and mixtures thereof. The preferred polar organic solvent is NMP due to its efficacy and commercial availability. The amount of solvent may vary, as is known in the art.

The order of addition of the materials used to prepare the poly (arylene sulfide ketones) may vary as desired.

In general, alkali metal sulfide (such as Na 2 S) and alkali metal hydrogen sulfide (such as NaSH) tax alkali metal hydroxide (such as NaOH) and alkali metal hydrogen sulfide (such as NaSH) and dihalobenzophenone (such as 4,4'-dichlorobenzophenone) can be added to the reaction vessel in any order. A polar organic solvent (such as NMP) is generally added to the reaction mixture following the addition of the above ingredients.

Although the reaction temperature at which the polymerization is carried out can vary within wide limits, it is generally about 125 to 450 ° C, more preferably about 175 to 350 ° C, more preferably about 225 to 275 ° C. The reaction time may vary widely depending in part on the reaction temperature, but is generally from about 10 minutes to about 72 hours, preferably from about 1 hour to about 20 hours. The pressure should be sufficient to maintain the reaction mixture essentially as a liquid phase. The pressure range is generally about 0-2068 kPa, preferably 1034 to about 1724 kPa.

If desired, the polymer can be recovered, preferably by removing the polymer and solvent from the cooled reactor and filtering the polymer. The polymer can be washed with water and dried in a vacuum oven.

The accompanying examples are intended to better support the understanding of the invention. In particular, the materials, species, and conditions used are intended to further illustrate the invention and not to limit its reasonable scope.

Example I. This example describes the preparation of poly (phenylene sulfide diketone) resin (PPSK) using equimolar amounts of NaSH and NaOH. A one-liter stainless steel reactor equipped with a double screw stirrer, a nitrogen inlet tube, and a fracture plate was charged with 41.63 g of sodium hydrogen sulfide flakes (containing 58.17 wt% NaSH, 0.35 wt% Na 2 S, and about 41.4 wt% Na 2 S). % by weight H2O), 17.58 g of sodium hydroxide pellet (98.2% by weight of NaOH, supplied by Mallinckrodt, Inc.,

St. Louis, Mo), 108.48 g of 4,4'-dichlorobenzophenone (DCBP, supplied by Aldrich Chemical Company, Milwaukee, Wisconsin)

II

90784 9 and 343 g (3.46 moles) of N-methyl-2-pyrrolidone (NMP). Thus, the same number of moles (0.432) of NaSH, NaOH and DCBPrt was charged and the molar ratio of H 2 O to NaSH (H 2 O: NaSH) was about 2.2: 1.

5

The reactor was sealed, alternatively pressurized using 689 kPa N and then a hole was opened to remove air. The reaction mixture was then stirred and heated to about 250 ° C (over one hour). These 10 temperatures were maintained for about three hours while a pressure of about 1241 kPa was established. The reactor was then cooled to about 200 ° C and 3 g of DCBP and 100 g of NMP were added to cover the formed PPSK polymer with DCBP. The contents of the reactor were reheated to a temperature of about 250 ° C and maintained at that temperature for about 1 hour.

The polymer of this series (Series 1) was removed from the cooled reactor, collected by filtration through a Buchner funnel 20, washed seven times with 2.5 L of separate hot deionized water (about 70 ° C) and dried in a vacuum oven at about 80 ° C. låmpåtilassa. The intrinsic viscosity (LV) of the PPSK polymer, measured at 30 ° C in a # 200 viscometer using a solution of 0.5% by weight with concentrated H 2 SO 4 as solvent, was 0.45.

In the second series (Series 2), an equimolar mixture of NaSH, NaOH, and DCBP in NMP was polymerized under essentially the same process conditions as above, except that NasH, NaOH, H 2 O, and NMP: The mixture was first dehydrated at 0 kPa and 160-205 ° C before all DCBP was added to the cooled reactor (about 105 ° C) and coating with DCBP was not performed. The reactor was then sealed and heated at 250 ° C and 35,896 kPa for three hours. The intrinsic viscosity of the washed and dried PPSK polymer was 0.28.

10

Series 3-8 describe the preparation of PPSK using added molar ratios of NaSH to NaOH, the procedure being otherwise essentially in accordance with the procedure of Series 1 (no dewatering, polymerization at 250 ° C for three 5 hours, coating with DCBP at 250 ° C). at one hour, molar ratio of H 2 O to NaSH (H, 0: NaSH) about 2.2: 1).

The results are summarized in Table I: 10

Table I

Series NaSH NaOH NaSH NaSH: NaOH Internal moles moles mole-to-molar ratio of viscosity 15% 1 0.432 0.432 0.0 1: 1 0.45 2 0.500 0.500 0.0 1: 1 0.28 3 0.434 0.432 0.5 1.005 : 1 0.49 20 4 0.432 0.426 1.4 1.014: 1 0.64 5 0.441 0.432 2.0 1.020: 1 0.73 6 0.443 0.432 2.5 1.025: 1 0.68 7 0.445 0.432 3.0 1.030: 1 0.77 8 0.449 0.432 4.0 1.039: 1 0.45 25 9 0.454 0.432 5.1 1.051: 1 0.33

Series 3-8 show that the low intrinsic viscosity of the polymer product obtained from the molar excess of the small amount of alkali metal hydrogen sulfide obtained when using a small amount is equal to or greater than the intrinsic viscosity of the polymer products obtained by using stoichiometry. (Series 9) alkali metal-35 thysulfide. The data shown in Figure 1 show that PPSK polymers with an intrinsic viscosity of at least 0.45 were obtained using a molar excess of NaSH (relative to NaOH) of about 0.4-3.8% in the reaction mixture.

40 Changes in temperature of the PPSK resin produced in Series 5 were measured using a Perkin-Elmer DAC-2C differential scanning calorimeter equipped with a computer-fed 90784 11 data system and a Perkin-Elmer TADS-1 monitor. The polymer sample was heated at a rate of 20 ° C / minute.

The results obtained were a glass transition temperature Tg = 144 ° C; ki-5 melting temperature Tc = 191 ° C; melting point Tm = 340 ° C; melt crystallization temperature (after cooling the melt) Tmc = 291 ° C.

Example II. This example describes the preparation of PPSK essentially according to the method of Series 1 (Example I) using Na 2 S flakes (rather than NaSH or NaOH). 56.88 g of sodium sulfide flakes (containing about 59.3% by weight of Na 2 S, about 1.3% by weight of NaSH and about 39.4% by weight of H 2 O, corresponding to 0.432 moles of Na 2 S and 0.013 moles of NaSH and 1.25 moles water) is reacted with 0.432 moles of DCBPr in the presence of 3.46 moles of NMP.

The NaSH present was equivalent to about 3% excess NaSH. The intrinsic viscosity of the molded PPSK resin (yield about 89 g) was 0.58. Therefore, the use of an alkali metal sulfide such as Na 2 Sm and a certain small excess of alkali metal hydrogen sulfide such as NaSHm is clearly effective in the field of application of this invention.

25

Example III. This example illustrates the vulcanization of PPSK in such a way that its molecular weight continues to increase. The dark resin prepared in series 6 was placed in a drying oven heated to 316 ° C. The intrinsic viscosity of polymer 30 increased from an initial value of 0.68 to 0.84 after 30 minutes and to 0.97 after 60 minutes. After heating for about 120 minutes, the polymer no longer dissolved in H 2 SO 4. It was found that during the vulcanization, gas was evolved from the polymer, especially during the first 35 hours.

Claims (11)

A process for the preparation of a high molecular weight poly (arylene sulfide ketone) by polymerizing equimolar amounts of polyhalobenzophenone 5 and an alkali metal sulfide in a reaction mixture, characterized in that the polymerization is carried out with alkali metal sulfide and alkali metal sulfide 1 -0.038: 1. 10 Process according to claim 1, characterized in that the alkali metal sulphide is prepared in situ from (a) alkali metal hydrogen sulphide and (b) alkali metal hydroxide and that said small stoichiometric excess of alkali metal hydrogen sulphide is obtained by using (b): and (a): n has an molar ratio of 1.004: 1 to 1.038: 1. Process according to Claim 1 or 2, characterized in that the polyhalobenzophenone used comprises dihalobenzophenone and the reaction mixture used comprises a polar reaction medium. Process according to Claim 1 or 3, characterized in that an alkali metal hydrogen sulphide is used in a ratio of 0.01: 1 to 0.035: 1 relative to said alkali metal sulphide. Process according to claim 2 or 3, characterized in that the alkali metal sulphide is prepared at site 30 from (a) alkali metal hydrogen sulphide and (b) alkali metal hydroxide and that said small stoichiometric excess of alkali metal hydrogen sulphide is obtained by using (a) and (b): n has an molar ratio of 1.01: 1 to 1.035: 1. Process according to one of the preceding claims, characterized in that the poly (arylene sulphide ketone) comprises poly (phenylene sulphide ketone). li 90784 Process according to Claim 6, characterized in that the poly (phenylene sulphide ketone) is represented by repeating units of the formula: 50 / sAsl s Process according to Claim 7, characterized in that the dihalobenzophenone used comprises 4,4'-di-chlorobenzophenone and the polar reaction medium used comprises N-methyl-2-pyrrolidone. Process according to Claim 6, characterized in that the intrinsic viscosity of the poly (phenylene sulphide ketone) is at least about 0.48 dl / g, measured at a temperature of 30 ° C in a viscometer no. 200 using a 0.5% by weight solution in concentrated H 2 SO 4 and that the intrinsic viscosity of the poly (phenylene sulfide ketone) is in particular 0.55-0.77 dl / g. Process according to any one of the preceding claims, characterized in that the polymerization conditions comprise a temperature range of 175 to 350 ° C, an overpressure of the pressure range of 0 to 1.38 MPa and a reaction time of 1 to 72 hours. Use of a poly (arylene sulfide ketone) obtained according to one of Claims 1 to 10 for the production of shaped articles, in particular fibers and films.